Process of making varnish-bases.



, UNITED STATES PATENT OFFICE.

GARLETON ELLIS AND'LOUIS RAIBINOVITZ, OF MONTCLAIR, NEW JERSEY,ASSIGNORS,

BY MESNE ASSIGNMENTS, OF FOUR-TENTHS T0 ELLIS-FOSTER COMPANY, A (JOB.-PORATION OF NEW JERSEY, AND SIX-TENTHS T0 INDESTRUCTIBLE PAINT COM-PANY, LTD., OF LONDON, ENGLAND, A CORPORATION. i a

PROCESS OF MAKING VARNISH-BASES.

No Drawing.

To all whom it may concern:

Be it known that we, CARLEToN ELLIS and LOUIS, RABINovrrz, citizens ofthe United States, and residents of Montclair, in the 5 county of Essexand State of New Jersey,

have invented certain new and useful Improvements in Processes of MakingVarnish- Bases, of which the following is a specifica= tion.

0 This invention relates to a method of making resin esters and to theproduct of such process and relates in particular to a method whichinvolves certain improved and 'simplified operations and enables esters,anhy- 5 drids, lactones and the like, in some cases of almost completeneutrality to be prepared.

Rosin and other varnish resins contain a large amount of acid, commonlyregarded as abietic and sylvic acids, so that the acid number ofcolophony is around 140 or 150 and this resin very readily unites withbasic bodies, such as white lead and zinc white, so that when rosin isused as a component of grinding varnish the pigment combines with theresin acid and livering results, causing deterioration, if not completeloss of the product. To ameliorate this difliculty to some extent, rosinhas been hardened by lime or other alkali which only partly neu- 0tralizes the acid. Lime resinate of a more neutral character would betoo slightly soluble in the vehicle, employed. Lime treatment therefore,does not overcome the difficulty. By esterifying resin with glycerin,

5 or other bodies containing thev hydroxyl group, including the alcoholsand also even that other class of hydroxylated bodies, the

phenols, esters can be obtained which do notreact deleteriously with thebasic pigment employed. As ordinarily prepared, however, these have thedisadvantage of containing a certain amount of free acid, as forexample, a commercial sample of rosin ester I which was found toiexhibitabout 18% 5. acidity. Furthermore, the present method of'making ester,or ester-gum, as it is known tothe trade, involves heating under apressure of several atmospheres, with for example, glycerin, and thendistilling by, the vac- 0 unm process, whlch involves a series ofoperations with a plant of a costly character.

Specification of Letters Patent.

Patented May 22, 1917.

Application filed December 29, 1914. Serial No. $179,557.

By the present invention it is possible to entirely eliminate theoperations under pressure and in 'vacuo, although these may be used withthe present process, if any advantage under special circumstances isderived by so doing. According to one form of the present inventioncolophony or various resins such as Kongo, Pontianak, kauri and othersimilar hard resins or gums may be treated with glycerin, or otherequivalent material in the presence of hydrochloric acid gas, or similargaseous dehydrating agent, preferably without the use of any solventvehicle. The reaction is usually best carried on by passing thedehydrating gas into direct contact with a molten mixture of the rosinand glycerin. The reaction temperature may be 280300 (1., and thehydrochloric acid which passes through the mass,

serves to withdraw the moisture and water produced. Any rosin spirits orother vola-';

tile material originally in the resin, or

A11 illustrative example is the following:

I. 50 parts of rosin and 5 to 8 parts by weight of a strong glycerinwasheated to 285 C.,'for two hours, while a current of hydrochloric acidgas was passed through the molten mass. In this way, the acid number ofthe resulting product was found to be reducedto 1/15 its original valueand 1 no hydrochloric acid was detectable in the finished product.mately that of the original rosin.

. Another method of preparation is that of violently agitating the rosinand the glycthe material into a spray or foam and brings The color wasapproxierin in a chamber through which hydrochloric acid gasis passed. Acylinder having a horizontal paddle wheel, which churns the hydrochloricacid gas into intimate contact with the material may be employed, orother suitable agitating devices may be used.

Or the gas may be passed through the resin v sandarac and the like, mayalso be treated in a like manner. Ordinary rosin may be treated moreeasily than, for example, Kongo gum, which material is diflicult offusion at moderate temperatures, except in lhe presence of the rosinwhich acts as a After the product has been treated in this manner, itmay be heated with hydrated lime, or other material of a basic nature toform some lime resinate from the remaining acid material.

By the action of carbon dioxid on'a mixture of rosin and glycerin, asubstantial reduction of the acid number is secured, as will beindicated by the following example i II. parts of rosin and 11 parts byweight of glycerin were heated to 290 C., and a stream of dry carbondioxid was bubbled through the molten mixture, for a period of one and aquarter hours. The rosin showed a drop in acidity to 18% of the originalacidity and the color of the product was very good. The carbon dioxidgas used was dried by passing through concentrated sulfuric acid andover calcium chlorid. In carrying out this operation on a manufacturingscale, the carbon dioxid gas may be circulated through the reactingresinous mass and when withdrawn, is passed through a drying chamber andthe like to remove moisture, and" any products of distillation ifdesired, and is then re turned to the body of molten resin so as totravel in a cyclic path, removing the moisture from the resin and inturn being freed from the mixture which it has picked up.

III. According to another example 12 parts of rosin and 1.8- partsofglycerin were heated for two and a half hours at 280300 (3., in a closedelectrically heated container fitted with a stirrer and through which astream of dried carbon 'dioxid was passed. The acid number of theresinous material fell by this treatment to nearly 10% of that of theoriginal resin.

By the action of hydrochloric acid, or

other similar or suitable dehydrating material on rosin alone withoutglycerin, a reno-. doubt to the formation of anhydrids,

periodjof one half hour,-while a stream duction' in the acid number isobtained, due

lalctones-land the like.

V. I'Foi .example, a quantity of rosin was dl toiabout 300 in" a closedcontainer of hydrochloric acid gas was passed through the molten rosinand it was found that the is heated and the mixture esterified by simpleheating, or by the gas treatment, or otherwise, as hereinbefore setforth.

When combining rosin and glycerin considerable foaming occurs when atemperature of 175-220 or so is reached and it is usually desirable toheat to about 250 C. before introducing the gas current to avoid unduefoaming and to thus avoid carrying over some portion of the heated massinto the receiver.

Non-oxidizing gases such as carbon monoxid or dioxid, nitrogen, hydrogenand even the vapors of volatile hydrocarbon such as gasolene or benzolare usually to be preferred to hydrochloric acid gas as the latter oftenexerts a softening effect on rosin which is not desired in the hardertypes of varnish compositions.

' Chlorin gas may be passed through solutions of rosin in a suitablesolvent either to bleach the resinous material or to add or substitutechlorin. When chlorin is passed into melted rosin darkening occurs butin solution in a solvent such as carbon tetrachlorid some bleachingtakes place.

A product suitable for general use is prepared by esterifying rosin toan acid number of about 1/5 the normal and then combining about 2% oflime therewith.

A varnish ester or other resin or composite resin esters or rosinanhydrid or similar product of the process herein set forth may bemelted and incorporated with varnish oils such as boiled or oxidizedlinseed or Chinese wood oil, or perilla oil and in some cases fish orwhale oils and the semi-drying oils, such as cottonseed, corn, rape andthe like. When the drying features of the oils are not taken intoconsideration, mineral oil may be introduced more or less. Thecomposition is made up with varying proportions of the oil and resinousmaterial, using a larger proportion to make the long oil varnishes andsmaller proportions of oil in the case of short oil varnishes. Whenprepared for use as a varnish where the acidity of the composition isnot a factor, various acid resins or otherwise, may be incorporated withthe composition. When used for grinding va' i'- nishes, the compositionshould be sufliciently neutral to avoid any undesirable livering and maybe ground with the pigments, such a paste or composition of theconsistency desired. Suitable driers and also thinners I such asturpentine, benzin, benzol, toluol and the like may be introduced in thedesired amount. A composition prepared from the rosin or anhydrid may beheated finally with a small amount of lime so as to contain some limeresinate, or if desired zinc resinate is incorporated with about anwhich comprises forming the anhydrid of rosin and heating such anhydridwith glycerin under substantially ordinary atmospheric pressure; wherebythe rosin ester of glycerin is obtained.

2. The process of making a varnish material which comprises forming theanhydrid of rosin and heating such anhydrid with an organic hydroxy bodyunder substantially ordinary atmospheric pressure; whereby the rosinester is obtained.

3. The process of making a varnish composition which comprisesdehydrating rosin by heating and passing an acid gas there through.

4. The process of making a varnish ma- .by heating and passing carbonicacid gas therethrough.

6. The process of'making a varnish material which comprises forming theanhydrid of rosin and heating such anhydrid with glycerin to 300 C.;whereby the rosin ester of glycerin is obtained.

7 The process of making resin esters which comprises heating andagitating a mixture of resin and a body capable of esterifying therewithwhile contacting with these a gaseous medium capable of aiding in theesterification.

8. The process of making resin esters which comprises heating andagitating a mixture of resin and a body capable of esble of aiding inthe esterification.

9. The process of making an artificial varnish gum which comprisesforming the anhydrid of a resin and heating such anhydrid with glycerinto 300 0.; whereby 'a resin ester composition is obtained.

10. The process of making resin esters which comprises heating andagitating a mixture of rosin and glycerin while contacting with these agaseous medium' capable of aiding. in the esterification.

11. The process of making resin esters which comprisesheating andagitating a mixture of resin and a body capable of esterifying therewithcomprising glycerin while contacting with these an inert gaseous mediumcapable ofi'aiding in the removal of moisture.

12. The process of making resin esters which comprises passing adehydrating gas through the resin and a body capable of esterifying withthe resin acid thereof.

13. The process of making resin esters which comprises bringingheat-modified resinous material and a body capable of esterifyingtherewith into intimate contact at an elevated temperature and atsubstantially atmospheric pressure and in maintaining such conditionsuntil a substantial degree of esterification results.

14. The process of making rosin esters.

which comprises passing a dehydrating gas through heated rosin and abody capable of esterifying with the resin acid thereof.

15. The process of making resin esters which comprises bringingheat-modified resinous material and a body capable of esterifyingtherewith into intimate contact at about 300 C. and at substantiallyatmos pheric pressure and in maintaining such conditions until asubstantial degree of esterification results.

16. The process of making resin esters which comprises bringing resinousmaterial and a body capable of-esterifying therewith into contact at anelevated temperature and at substantially atmospheric pressure and inmaintaining such conditions until at least a 75% degree-ofesterification results.

17. The process of making resin esters comprising rosin which comprisespassingcarbon dioxid gas through the resin and a body capable ofesterifying with theresin acid thereof.

18. The process of making resin esters which comprises bringing resinousmaterial and a body capable of esterifying therewith into contact withagitation atan elevated temperature and at substantially atmosphericpressure andin maintaining such conditions until a substantial degree ofesterification results.

1 9. The process of making resin esters which comprises passing adehydrating gas through agitated resin and a body capable of esterifyingwith the resin acid thereof.

20. The process of making resin esters which comprises bringing resinousmaterial and a body capable of esterifying into violent contact at anelevated temperature and at substantially atmospheric pressure and inmaintaining such conditions until a substantialdegree of esterificationresults.

21. The process of making an artificial varnish gum which comprisesforming the anhydrid of a resin and esterifying such anhydrid withglycerin substantially without exposing the material tosuper-atmospheric pressure.

22. The process of'making varnish material which comprises heating resinto a high temperature to change its chemical constitution andesterifying-under substantially atmospheric pressure With glycerin.

28. The process of making varnish material which comprises heating resinto a high temperature to change its chemical constitution andesterifying under substantially atmospheric pressure with a body capableof forming an ester therewith.

24:. The process of making an artificial varnish gum which comprisesforming the anhydrid of a resin, in esterifying such anhydrid with anorganic hydroxy body capable of combining therewith and in allowing thewater formed by such reaction to freely escape from the reaction mass.

25., The process of making an artificial cape from the reaction mass.

27. The process of making an artificial varnish gum which comprisesheating a resinous body to a high temperature to change its chemicalconstitution, in esterifying with glycerin and in constantly removingthe moisture formed from the reaction zone.

Signed at Montclair, in the county of Essex and State of New Jersey,this 24th day of December A. D. 1914:.

CARLET ON ELLIS. LOUIS RABINOVITZ.

Witnesses:

Emu CURTIs, W. 0. HENKE.

